U.S. patent number 5,824,415 [Application Number 08/602,727] was granted by the patent office on 1998-10-20 for decorative material.
This patent grant is currently assigned to Dai Nippon Printing Co., Ltd.. Invention is credited to Tadamichi Ishii, Masahiro Kanki, Masaki Tsukada.
United States Patent |
5,824,415 |
Kanki , et al. |
October 20, 1998 |
Decorative material
Abstract
The present invention relates to a decorative material which is
excellent in surface properties such as scratch resistance and soil
resistance and, at the same time, environmentally friendly. The
decorative material meludes: a substrate of a thermoplastic resin;
and a resin layer 3 provided on one side of the substrate through a
heat-sensitive adhesive layer 2, the resin layer being formed of a
resin of a copolymer, of ethylene with an
.alpha.,.beta.-unsaturated carboxylic acid, which has been
partially or completely neutralized with a metal ion.
Inventors: |
Kanki; Masahiro (Tokyo-To,
JP), Tsukada; Masaki (Tokyo-To, JP), Ishii;
Tadamichi (Tokyo-To, JP) |
Assignee: |
Dai Nippon Printing Co., Ltd.
(JP)
|
Family
ID: |
27463324 |
Appl.
No.: |
08/602,727 |
Filed: |
April 25, 1996 |
PCT
Filed: |
June 20, 1995 |
PCT No.: |
PCT/JP95/01217 |
371
Date: |
April 25, 1996 |
102(e)
Date: |
April 25, 1996 |
PCT
Pub. No.: |
WO95/35210 |
PCT
Pub. Date: |
December 28, 1995 |
Foreign Application Priority Data
|
|
|
|
|
Jun 22, 1994 [JP] |
|
|
6-162931 |
Jun 22, 1994 [JP] |
|
|
6-162932 |
Jun 22, 1994 [JP] |
|
|
6-162933 |
Mar 15, 1995 [JP] |
|
|
7-056321 |
|
Current U.S.
Class: |
428/411.1;
428/206; 428/172; 428/542.2; 525/419; 156/244.11; 525/502; 525/183;
428/343; 428/207; 428/202; 428/159; 428/95; 428/200 |
Current CPC
Class: |
B32B
37/153 (20130101); B32B 27/32 (20130101); B32B
27/308 (20130101); B32B 38/14 (20130101); B32B
7/12 (20130101); B32B 27/08 (20130101); B44C
5/0446 (20130101); Y10T 428/24901 (20150115); B32B
2451/00 (20130101); Y10T 428/24504 (20150115); Y10T
428/28 (20150115); Y10T 428/2486 (20150115); Y10T
428/23979 (20150401); Y10T 428/31504 (20150401); Y10T
428/24612 (20150115); Y10T 428/24843 (20150115); Y10T
428/24893 (20150115) |
Current International
Class: |
B32B
27/08 (20060101); B44C 5/04 (20060101); B44C
5/00 (20060101); B32B 38/14 (20060101); B32B
009/00 () |
Field of
Search: |
;428/200,187,202,343,347,411.1,206,95,207,172,483,290,195,159,542.2
;156/244.11 ;525/502,419,183 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
|
|
|
|
|
|
|
1-226325 |
|
Sep 1989 |
|
JP |
|
3-24942 |
|
Feb 1991 |
|
JP |
|
4-64441 |
|
Feb 1992 |
|
JP |
|
Primary Examiner: Ryan; Patrick
Assistant Examiner: Bahta; Abraham
Attorney, Agent or Firm: Parkhurst & Wendel, L.L.P.
Claims
We claim:
1. A decorative material comprising:
a substrate comprising a thermoplastic resin;
a heat-sensitive adhesive layer formed on one side of said
substrate, said heat-sensitive adhesive layer comprising a random
copolymer of an olefin with methacrylic acid or a random copolymer
of an olefin with acrylic acid, wherein carboxyl groups present
randomly in molecules of the copolymer are crosslinked among the
molecules through hydrogen bonding; and
a resin layer provided on said substrate through said
heat-sensitive adhesive layer, said resin layer being formed of a
resin of a copolymer of ethylene with an
.alpha.a,.beta.-unsaturated carboxylic acid, which has been
partially or completely neutralized with a metal ion.
2. The decorative material according to claim 1, further comprising
a pattern layer.
3. The decorative material according to claim 1, further comprising
a backer layer laminated thereon.
4. The decorative material according to claim 1, wherein said resin
layer is formed of a resin of a copolymer of ethylene with acrylic
acid or ethylene with methacrylic acid, which has been neutralized
with a metal ion to a degree of ionization of 5 to 80%.
5. A process for producing a decorative material, comprising the
steps of:
forming a pattern layer on one side of a substrate;
forming a heat-sensitive adhesive layer on the substrate to cover
the pattern layer, the heat-sensitive adhesive layer comprising a
random copolymer of an olefin with methacrylic acid or a random
copolymer of an olefin with acrylic acid, wherein carboxyl groups
present randomly in molecules of the copolymer are crosslinked
among the molecules through hydrogen bonding;
forming a resin layer over the heat-sensitive adhesive layer, the
resin layer being formed of a resin of a copolymer of ethylene with
an .alpha.,.beta.-unsaturated carboxylic acid, which has been
partially or completely neutralized with a metal ion; and
bonding and integrating the resin layer with the substrate, pattern
layer and heat-sensitive adhesive layer to obtain the decorative
material.
6. The process according to claim 5, wherein the heat-sensitive
adhesive layer is provided by extrusion coating.
7. The process according to claim 5, further comprising the step of
laminating a backer layer on the substrate remote from the pattern
layer.
8. The process according to claim 5, wherein the resin layer is
formed of a resin of a copolymer of ethylene with acrylic acid or
ethylene with methacrylic acid, which has been neutralized with a
metal ion to a degree of ionization of 5 to 80%.
9. The process according to claim 7, wherein the bonding of the
resin layer and the lamination of the backer layer are carried out
in a single step.
Description
BACKGROUND OF THE INVENTION
The present invention relates to decorative materials, such as
floor coverings, and more particularly to decorative materials,
having high properties, which can be used as an alternative to
vinyl chloride resin floor coverings which causes environmental
pollution.
A large number of floor coverings using a polyvinyl chloride film
as a top film have hitherto been used in the art. The floor
coverings using a polyvinyl chloride film as the top film, however,
had the following drawbacks.
(1) The surface thereof has unsatisfactory abrasion resistance.
(2) Incineration results in the formation of a chlorine
compound.
(3) Since the transparency and brilliance are unsatisfactory, the
commercial value as the floor covering is still unsatisfactory.
(4) The soil resistance is so low that, once the surface is soiled,
it is difficult to remove the soil.
In particular, the incineration of waste of the polyvinyl chloride
film, which has hitherto been used as a decorative material, poses
problems of corrosion of an incinerator by a hydrogen chloride gas
and a chlorine gas evolved during the incineration and the
evolution of a strongly acidic gas. Solving the above problems
unfavorably incurs an increase in waste disposal cost.
In order to reduce the above problem, an attempt has been made to
reduce the chlorine content of the decorative material by forming
the surface layer of the printed decorative face through coating of
a solvent-soluble resin varnish instead of the use of a transparent
vinyl chloride film. The formation of the surface layer by coating
of the solvent-soluble resin varnish is advantageous in that a
surface protective coating can be formed simply by evaporating the
solvent to dry the coating. The resultant decorative material,
however, is unsatisfactory in surface properties such as surface
hardness, gloss, abrasion resistance, and chemical resistance.
DISCLOSURE OF INVENTION
Accordingly, an object of the present invention is to provide a
decorative material which is excellent in surface properties, such
as scratch resistance and soil resistance, and, at the same time,
environmentally friendly.
In order to attain the above object, the decorative material of the
present invention comprises: a substrate of a thermoplastic resin;
and a resin layer provided on one side of the substrate through a
heat-sensitive adhesive layer, the resin layer comprising a
copolymer of ethylene with an .alpha.,.beta.-unsaturated carboxylic
acid, the copolymer being partially or completely neutralized with
a metal ion.
In the present invention, a pattern layer and a backer may be
suitably laminated according to the purposes.
The process for producing a decorative material according to the
present invention comprises the steps of: forming a pattern layer
on one side of the substrate and a heat-sensitive adhesive layer
provided on the other side of the substrate; and putting a resin
film formed of a resin of a copolymer, of ethylene with an
.alpha.,.beta.-unsaturated carboxylic acid, which has been
partially or completely neutralized with a metal ion, on the top of
the laminated substrate in such a manner that the resin film faces
the heat-sensitive adhesive layer, and bonding and integrating the
resin film with the laminated substrate.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a cross-sectional view of an embodiment of the decorative
material according to the present invention.
BEST MODE FOR CARRYING OUT THE INVENTION
As shown in FIG. 1, the decorative material according to the
present invention comprises: a substrate 1 of a thermoplastic
resin; and a resin layer 3 provided on one side of the substrate
through a heat-sensitive adhesive layer 2, the resin layer being
formed of a resin of a copolymer, of ethylene with an
.alpha.,.beta.-unsaturated carboxylic acid, which has been
partially or completely neutralized with a metal ion.
Further, in the present invention, a pattern layer 4 and a backer
layer 5 may be provided.
In the decorative material of the present invention, the resin
layer 3 is formed of a resin film of a copolymer, of ethylene with
an .alpha.,.beta.-unsaturated carboxylic acid, which has been
partially or completely neutralized with a metal ion (such a resin
being hereinafter referred to as an "ionomer."
Specific examples of the ionomer film include films based on
polyolefins, such as polyethylene, polypropylene, and polybutylene.
The film used in the present invention is one formed from a resin
having such a structure that part of carboxyl groups are
crosslinked with molecular chains of the polyolefin through a metal
ion among the molecular chains.
The above ionomer film does not evolve any chlorine compound during
combustion and, hence, is environmentally friendly. Preferably, the
ionomer film can be laminated to and integrated with a plywood or
other plastic sheets through an adhesive layer and has high
transparency and, at the same time, excellent abrasion resistance,
chemical resistance, and oil resistance.
Examples of the metal ion generally used for the neutralization
include Cu.sup.++, Ag.sup.+, Na.sup.+, and Zn.sup.++. Among them,
Na.sup.+ and Zn.sup.++ are preferred because they are excellent in
chemical and physical properties such as oil resistance, soil
resistance, ductility, strength, transparency, and abrasion
resistance.
For example, SURLYN (trade name, Du Pont-Mitsui Polychemical Co.,
Ltd.), Himilan (trade name, Du Pont-Mitsui Polychemical Co., Ltd.)
and the like may be used.
Acid moieties in the copolymer of an olefin with an
.alpha.,.beta.-unsaturated carboxylic acid used in the present
invention include acrylic acid and methacrylic acid. The copolymer
is preferably such that the acid moiety is acrylic acid and the
degree of ionization is 5 to 80%. When the degree of ionization is
less than 5%, the film strength is likely to be lowered. On the
other hand, a degree of ionization of more than 80% is unfavorable
because working properties, such as hot pressing and embossing, are
likely to be lowered.
A film of the ionomer can be formed by blow molding (an inflation
process) using a circular die, melt extrusion using a T-die (a
T-die process), or melt extrusion coating.
A sheet prepared by blow molding using a circular die utilizes air
cooling, resulting in somewhat poor gloss and transparency.
However, it is advantageous in that the sheet width is variable as
desired.
For the melt extrusion molding using a T-die, since rapid cooling
using a cooling roll is possible, it is possible to form a sheet
having excellent gloss and transparency and, further, to impart a
relief pattern layer to the sheet using a cooling roll having a
surface appearance suitable for this purpose. This method, however,
is disadvantageous in that the variability of the sheet width is
limited.
The thickness of the ionomer film is preferably in the range of
from 20 to 200 .mu.m which causes no problems in treatments after
the formation of the film, such as printing and embossing.
Preferably, the pattern layer may be provided on the ionomer film
by a transfer process described below. In this case, if necessary,
the ionomer film is preferably subjected to corona discharge
treatment from the viewpoint of enhancing the bond strength between
the ionomer film and other layer(s). In the corona discharge
treatment, the application of a high voltage at a high frequency to
a gap between an electrode directly connected to the high voltage
and a metallic roll coated with a silicone results in the
occurrence of a high-voltage corona. When the film is travelled
through this place at a constant speed, it is reacted with ozone
and nitrogen oxide to form a carbonyl group or the like, rendering
the film hydrophilic. At the same time, the discharge creates a
rough surface utilizing a numerous number of pores and, in
addition, treats a monomeric substance present in the surface of
the film to improve the adhesion of the ionomer film to a printing
ink or the like, realizing high bonding strength.
The degree of the corona discharge treatment is preferably such
that the surface tension of the treated surface is 46 to 50 dyn/cm.
When the surface tension is more than 50 dyn/cm, there is a
possibility that blocking occurs at the time of take-up procedure
and arc discharge creates pinholes in the resin layer. When the
surface tension is less than 46 dyn/cm, the adhesion of the
printing ink to the film is unstable and, at the same time, no
satisfactory adhesion to other substrate(s) after the formation of
the film can be attained.
Incorporation of an antistatic agent into the ionomer film is
preferred because the creation of static electricity by friction
can be prevented when the decorative material is used as a floor
covering. Antistatic agents usable herein include cationic
surfactants, amphoteric surfactants, anionic surfactants, and
nonionic surfactants, for example, organotin compounds.
The substrate of the decorative material according to the present
invention comprises a thermoplastic resin sheet. In this case,
preferred examples of the thermoplastic resin include polyolefins
such as polyethylene, polypropylene, polybutylene,
polymethylpentene, and ionomers; vinyl resins (except for polyvinyl
chloride) such as polyvinyl acetate, polyvinyl alcohol, ethylene,
and vinyl alcohol copolymer resins; polyester resins such as
polyethylene terephthalate, ethylene terephthalate isophthalate
copolymer, polybutylene terephthalate, and polycarbonate; styrene
resins or styrene copolymers such as polystyrene,
poly-.alpha.-methylstyrene, (meth)acrylate/styrene,
acrylonitrile/styrene, and ABS (acrylonitrile/butadiene/styrene
copolymer); acrylic resins such as polymethyl methacrylate,
polyethyl methacrylate, polybutyl methacrylate, polymethyl
acrylate, polyethyl acrylate, and polybutyl acrylate; polyamides
such as nylon 6 and nylon 66; and other resins such as polyimides
polyphenylene oxide, polysulfone, and vinyltoluene resin.
When the substrate is formed of a resin having a melting point
above the melting point of the resin constituting the ionomer film
of the present invention, the use of a resin having a melting point
above 87.degree. to 99.degree. C., i.e., the melting point of the
ionomer film, is preferred. Further, materials having excellent
printability and transparent or colored sheets may be selected
according to the purposes.
When the melting point of the resin constituting the substrate is
below the melting point of the ionomer film, melt extrusion coating
of a resin for the ionomer film in the formation of a film results
in melt breaking or unfavorably provides a film having poor
printability. Among the exemplified resins, polypropylene,
medium-density polyethylene, polyester, polyamide and the like are
particularly preferred for the substrate. They may be used as a
stretched or unstretched film.
The provision of a pattern layer (a print layer), which is
excellent as a design and, at the same time, has excellent hiding
power, on at least one side of the substrate enables the pattern
layer seen through a transparent film including an ionomer film to
have an excellent print effect.
In the present invention, the ionomer film is bonded to and
integrated with one side of the substrate through a heat-sensitive
adhesive layer.
The heat-sensitive adhesive used in the present invention is an
adhesive which can develop adhesive action upon heating. Examples
thereof include petroleum resins and ketone resins known to soften
upon heating. The term "heat-sensitive adhesive" used herein is
intended to mean adhesives including a hot melt adhesive, that is,
an adhesive which becomes liquid upon heating and, upon subsequent
cooling to room temperature, is solidified to develop adhesive
properties.
The use of the heat-sensitive adhesive in the decorative material
of the present invention offers advantages including that high
adhesion can be attained between the ionomer sheet as a top sheet
and the thermoplastic resin sheet and that an adhesive layer,
together with a pattern layer, can be previously formed on a
thermoplastic resin sheet by continuous take-up procedure and
stored in a roll form, making it possible to eliminate the step of
applying an adhesive at the time of subsequent hot pressing for
lamination and integration in a sheet form.
Specific examples of the heat-sensitive adhesive usable in the
present invention include any thermoplastic resin having the above
properties, and, among them, polyolefin resins (except for vinyl
chloride resins causative of environmental pollution), such as
polyethylene, ethylene copolymer resin, and ionomers are
suitable.
A resin of a random copolymer of an olefin with methacrylic acid or
an olefin with acrylic acid, wherein carboxyl groups present
randomly in molecules are crosslinked among molecular chains
through hydrogen bonding, is best suited as a heat-sensitive
adhesive having high strength of bonding to the ionomer resin sheet
and excellent suitability for coating by extrusion coating.
Examples of such copolymer resins usable in the present invention
include ethylene/methacrylic acid copolymer resin,
propylene/methacrylic acid copolymer resin, butene/methacrylic acid
copolymer resin, ethylene/methacrylic acid copolymer,
propylene/acrylic acid copolymer, and butene/acrylic acid
copolymer.
Among them, ethylene/methacrylic acid copolymer resin or
ethylene/acrylic acid copolymer resin, of which the melting point
is 90.degree. to 100.degree. C., is preferred.
The above heat-sensitive adhesive, even in the case of a decorative
material including an ionomer film, can develop a good adhesive
power of not less than 2 kg/inch of width in terms of peel
strength, which is adhesive power specified in JIS-A5705 as
necessary for practical use.
The ionomer film, when used as an alternative to a vinyl chloride
film, has excellent surface properties and, further, is
environmentally friendly. However, it, when used in a decorative
material, has poor adhesion to other constituent layer(s) (a
substrate or a pattern layer) and poor printability. Therefore, the
ionomer film causes various problems when it as such is used as a
decorative material.
In the present invention, the use of the above heat-sensitive
adhesive for bonding between the ionomer film and other constituent
layer(s) is preferred in order to eliminate the above problem.
In the present invention, the pattern layer may be formed by
conventional printing. Alternatively, it may be formed by a
transfer process.
For example, it may be formed by laminating a pattern layer and an
adhesive layer in that order on a transfer substrate sheet to
prepare a transfer sheet, heat-pressing the transfer sheet against
an object so as for the adhesive layer to face the object, and
peeling off the transfer substrate sheet.
The pattern layer may be formed by conventional printing. In the
decorative material of the present invention, the pattern layer may
be provided on any of the ionomer layer and the substrate.
Regarding the transfer substrate sheet used in the transfer sheet,
a sheet having excellent printability such as will not cause melt
breaking upon exposure to heat during the transfer is selected from
materials usable in the conventional transfer sheets.
For example, a stretched or unstretched sheet of a polyester, a
polyamide, polypropylene or the like and a laminate of this sheet
and paper or a nonwoven fabric may be usable. The thickness of the
substrate transfer sheet is preferably as small as 5 to 50 .mu.m
which causes no printing trouble because no uneven heating occurs
at the time of transfer of the pattern layer, enabling the pattern
layer to be uniformly adhered to the object.
The printing ink used in the pattern layer of the transfer sheet
may be any ink so far as it has suitable releasability from the
transfer substrate sheet. The releasability of the pattern layer is
determined by the transfer substrate sheet and a spreading agent
used in the ink. A suitable spreading agent may be selected from
linear polyesters, polyvinyl butyral, ethyl cellulose, rosin
derivatives, alkyl esters of polyacrylic acid, alkyl esters of
polymethacrylic acid, vinyl chloride/vinyl acetate copolymer,
chlorinated polyethylene, and chlorinated polypropylene. A resin
free from chlorine is, of course, preferred from the viewpoint of
the object of the present invention. Since, however, the spreading
agent used in the pattern layer is very small, the use of a
chlorine-containing resin does not substantially sacrifice the
effect of the present invention.
The adhesive layer used in the transfer sheet is heat-bonded
together with the material to be transferred, thereby transferring
and bonding the pattern layer to the object and may be formed of a
material selected from a linear polyester, acryl, polyurethane,
vinyl chloride/vinyl acetate copolymer, chlorinated polyethylene,
chlorinated polypropylene and the like. When the pattern layer is
transferred to the ionomer layer, the use of the above
heat-sensitive adhesive is preferred. As with the spreading agent,
the adhesive layer is preferably formed of a resin free from
chlorine.
In the present invention, for example, a backer is preferably
laminated to the pattern layer optionally through a primer
layer.
The backer is a material which serves to further increase the
thickness of the surface protective layer of the pattern layer,
thereby further enhancing the abrasion resistance of the pattern
layer, in cooperation with the ionomer layer. It is a matter of
course that the same effect can be attained by mere increase in
thickness of the ionomer layer. Since, however, the abrasion
resistance depends greatly upon the thickness of the surface layer,
if the enhancement of the abrasion resistance is contemplated, it
is preferred that the layer of an ionomer, which is a special
material, have a minimum thickness necessary as the outermost layer
with a general-purpose, low-cost resin layer being used for
increasing the thickness to a value large enough to enhance the
abrasion resistance.
Rubber, a polyolefin resin and the like are generally used as the
backer. In the present invention, the use of a backer of an olefin
resin, such as polyethylene, polypropylene, or polybutylene, is
preferred.
Further, in the present invention, if necessary, an EC (melt
extrusion coating) resin layer (not shown) may be provided between
the resin layer 3 and the heat-sensitive adhesive layer 2.
When the EC resin layer is provided, the provision of an anchor
coating layer is preferred in order to improve the bonding strength
between the resin layer 3 and the EC resin layer. For example, an
alkyl titanate anchor coating compound and a urethane anchor
coating compound may be used for this purpose.
The EC and anchor coating may be carried out, for example, by
coating an anchor coating compound on a substrate, drying the
coating to remove the solvent, continuously conducting EC thereon,
providing the heat-sensitive adhesive layer 2 and, if necessary,
conducting aging treatment.
Further, in the present invention, if necessary, a primer layer may
be provided from the viewpoint of improving the adhesion between
layers. The primer layer may be formed of the same resin as used in
the formation of the adhesive layer. For example, varnishes, such
as polyester/isocyanate, polyether/isocyanate, acrylic resin,
polyurethane, cellulose derivatives, and polyisocyanate, may be
used alone or as a mixture of two or more.
In the present invention, the step of forming a pattern layer on
one side of a substrate and forming a heat-sensitive adhesive layer
on the other side of the substrate is carried out separately from
the step of putting an ionomer film on the top of the above
substrate so as for the ionomer film to face the heat-sensitive
adhesive layer and bonding and integrating the two elements.
Further, in the present invention, the heat-sensitive adhesive
layer is preferably formed by extrusion coating.
Further, in the present invention, it is also possible to carry
out, as a single step, the step of bonding and integrating the
ionomer film with the substrate and the step of laminating the
backer. If necessary, the surface of the ionomer film may be
embossed.
The present invention will now be described with reference to the
following production examples, though it is not limited to the
description of these examples.
EXAMPLE 1
A pattern layer was gravure-printed using a two-component curable
polyurethane ink (trade name: ALFA, manufactured by Inctec Inc.,
Japan) on a surface, embossed in a matte form, of a 50 .mu.m-thick
ethylene/methacrylic acid random copolymer sheet (trade name:
NUCREL, manufactured by Du Pont-Mitsui Polychemical Co., Ltd.). A
chlorinated polypropylene resin liquid (trade name: LDK-TR,
manufactured by Inctec Inc.) was then coated on the pattern layer
to form a primer layer.
Thereafter, a 200 .mu.m-thick backer of an olefin was put on the
pattern layer side of the ethylene methacrylic acid copolymer
sheet, and a 200 .mu.m-thick ionomer film (trade name: Himilan,
manufactured by Du Pont-Mitsui Polychemical Co., Ltd.) was put on
the ethylene/methacrylic acid copolymer sheet in its side remote
from the pattern layer. Hot pressing was then carried out under
conditions of 140.degree. C. and 5 kg/cm.sup.2 for 10 min, thereby
preparing a decorative material.
An abrasion resistance test specified in JIS-A5705 was carried out
under conditions of abrasive paper S-42, truck wheel diameter 5 cm,
load 1 kg, and 1000 revolutions. As a result, the abrasion loss was
found to be 0.12 g. For comparison, the abrasion resistance test
was carried out for a conventional decorative material having a
polyvinyl chloride resin sheet as the surface sheet under the same
conditions, and the abrasion loss was found to be 0.25 g,
confirming that the decorative material of the present invention is
superior in abrasion resistance to the conventional decorative
material and free from any fracture such as caused by separation
between layers.
EXAMPLE 2
A pattern layer was gravure-printed using a two-component curable
polyurethane ink (trade name: ALFA, manufactured by Inctec Inc.) on
one side of a 25 .mu.m-thick polyethylene terephthalate film with
an adhesive layer provided on both sides thereof (trade name:
T-600WE, manufactured by Diafoil Co., Ltd.). A chlorinated
polypropylene resin liquid (trade name: LOLK-TR, manufactured by
Inctec Inc.) was then coated on the pattern layer to form a primer
layer.
Thereafter, a two-component curable polyurethane resin liquid
(trade name: Urethane Primer, manufactured by Dainichiseika Color
& Chemicals Manufacturing. Co., Ltd.) was coated on the
polyethylene terephthalate film in its side remote from the pattern
layer to form a primer layer.
A 200 .mu.m-thick backer of an olefin was put on the pattern layer
side of the polyethylene terephthalate film, and a 200 .mu.m-thick
ionomer film (trade name: Himilan, manufactured by Du Pont-Mitsui
Polychemical Co., Ltd.) was put on the primer layer. Hot pressing
was then carried out under conditions of 140.degree. C. and 5
kg/cm.sup.2 for 10 min, thereby preparing a decorative
material.
An abrasion resistance test specified in JIS-A5705 was carried out
under conditions of abrasive paper S-42, truck wheel diameter 5 cm,
load 1 kg, and 1000 revolutions. As a result, the abrasion loss was
found to be 0.12 g. For comparison, the abrasion resistance test
was carried out for a conventional decorative material having a
polyvinyl chloride resin sheet as the surface sheet under the same
conditions, and the abrasion loss was found to be 0.25 g,
confirming that the decorative material of the present invention is
superior in abrasion resistance to the conventional decorative
material and free from any fracture such as caused by separation
between layers.
EXAMPLE 3
A two-component curable polyurethane ink (trade name: ALFA,
manufactured by The Inctec Inc.) was coated on one side of a 25
.mu.m-thick polyethylene terephthalate film with an adhesive layer
provided on both sides thereof (trade name: T-600WE, manufactured
by Diafoil Co., Ltd.) to form a primer layer.
Then, an alkyl titanate anchor coating agent (trade name: B-1,
manufactured by Nippon Soda Co., Ltd.) was coated on the
polyethylene terephthalate film in its side remote from the pattern
layer, and the coating was dried to remove the solvent. A 20
.mu.m-thick ethylene/methacrylic acid random copolymer resin (trade
name: NUCREL, manufactured by Du Pont-Mitsui Polychemical Co.,
Ltd.) layer was formed thereon by continuous extrusion coating.
Thereafter, a 200 .mu.m-thick backer of an olefin was put on the
pattern layer side of the polyethylene terephthalate film, and a 20
.mu.m-thick ionomer film (trade name: Himilan, manufactured by Du
Pont-Mitsui Polychemical Co., Ltd.) was put on the
ethylene/methacrylic acid copolymer resin layer side. Hot pressing
was then carried out under conditions of 140.degree. C. and 5
kg/cm.sup.2 for 10 min, thereby preparing a decorative
material.
An abrasion resistance test specified in JIS-A5705 was carried out
under conditions of abrasive paper S-42, truck wheel diameter 5 cm,
load 1 kg, and 1000 revolutions. As a result, the abrasion loss was
found to be 0.12 g. For comparison, the abrasion resistance test
was carried out for a conventional decorative material having a
polyvinyl chloride resin sheet as the surface sheet under the same
conditions, and the abrasion loss was found to be 0.25 g,
confirming that the decorative material of the present invention is
superior in abrasion resistance to the conventional decorative
material and free from any fracture such as caused by separation
between layers.
EXAMPLE 4
A 50 .mu.m-thick acrylic resin film (trade name: HBS006,
manufactured by Mitsubishi Rayon Co., Ltd.) was used instead of the
polyethylene terephthalate film used in Example 3, and a pattern
layer was gravure-printed using a two-component curable
polyurethane ink (trade name: ALFA, manufactured by Inctec Inc.) on
one side of the acrylic resin film. Further, a chlorinated
polypropylene resin liquid (trade name: LDK-TR, manufactured by The
Inctec Inc.) was coated on the pattern layer to form a primer
layer.
Thereafter, a two-component curable polyurethane anchor coating
agent (trade name: Anchor Agent, manufactured by Showa Ink Ind.
Co., Ltd.) was coated on the acrylic resin film in its side remote
from the pattern layer, and the coating was dried to remove the
solvent. A 20 .mu.m-thick ethylene/methacrylic acid random
copolymer resin (trade name: NUCREL, manufactured by Du Pont-Mitsui
Polychemical Co., Ltd.) layer was formed thereon by continuous
extrusion coating. Aging was carried out at 40.degree. C. for one
day, and the procedure of Example 3 was repeated to prepare a
decorative material.
EXAMPLE 5
A decorative material was prepared in the same manner as in Example
3, except that a 50 .mu.m-thick ethylene/vinyl alcohol copolymer
resin film (trade name: Eval EF-E, manufactured by Kuraray Co.,
Ltd.) was used instead of the polyethylene terephthalate film.
EXAMPLE 6
A decorative material was prepared in the same manner as in Example
3, except that a 50 .mu.m-thick moldable polyethylene terephthalate
film (trade name: T-92, manufactured by Teijin Ltd.) was used
instead of the polyethylene terephthalate film.
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